2,3-dimethylmaleimido-alkyl haloacetates

ABSTRACT

2,3-Dimethylmaleimido-alkyl or oxaalkyl haloacetates are useful in the preparation of polymers containing maleimide groups and quaternary ammonium groups which polymers are soluble in water. The polymers can be used as light-sensitive photographic recording materials which can be developed with water.

This is a divisional of application Ser. No. 492,853, filed on May 9,1983, now U.S. Pat. No. 4,544,621, issued on Oct. 1, 1985.

The present invention relates to photocrosslinkable water-solublepolymers and copolymers which contain maleimidyl and quaternary ammoniumgroups, and to the use thereof as photographic recording material.

Photopolymers are used as photographic recording material using organicsolvents and aqueous bases or acids as developers. The processing ofsuch photopolymers suffers from the disadvantage that it necessitatesthe use of exhausting devices and that the working up of the developersis technically more complicated.

U.S. Pat. No. 4,229,519 and European patent application No. 0 029 358disclose water-soluble and water-developable photocrosslinkablecompositions which comprises photopolymers containing quaternaryammonium groups and ethylenically unsaturated groups. Thesephotopolymers can only be prepared by means of an uneconomic two-stepprocess (polymerisation and quaternisation). In addition, it isnecessary to use special photoinitiator systems so as to obtain asufficient light sensitivity. Further, such materials require inhibitorsto obtain a sufficient storage stability in the dark.

It is the object of the present invention to provide water-developablephotopolymers whose light sensitivity can be increased with knownphotoinitiators and which can be prepared in a single process step.

Accordingly, the present invention relates to homopolymers andcopolymers containing maleimidyl and quaternary ammonium groups andhaving a molecular weight of at least 1000, which polymers containstructural units of the formula I ##STR1## wherein R is a hydrogen atomor a methyl group,

Y is an oxygen atom or the --NH group,

A is a linear or branched C₂ -C₆ alkylene group,

R₁ and R₂ independently of each other are C₁ -C₄ alkyl or together aretetramethylene, pentamethylene or 3-oxapentylene,

D is C₁ -C₄ alkyl or a radical of the formula ##STR2## wherein R³ isalkylene, oxaalkylene or benzylene, R⁴ is a hydrogen atom or C₁ -C₄alkyl, R⁵ is a bivalent aliphatic, cycloaliphatic or aromatichydrocarbon radical or a bivalent aliphatic or aromatic heterocyclicradical containing up to 18 carbon atoms, and R⁶ has the meaning of R⁵or is ##STR3## wherein x is a value from 1 to 29 and R⁴ is a hydrogenatom or C₁ -C₄ -alkyl; and T₁ and T₂ independently of each other are C₁-C₄ alkyl or together are unsubstituted or C₁ -C₄ alkyl-substitutedtrimethylyene or tetramethylene, and

Z.sup.⊖ is an anion, with the proviso that, if D is C₁ -C₄ alkyl,structural units of at least one ethylenically unsaturated monomer whichcarries a maleimidyl group of the formula ##STR4## are present, andadditional structural units which are derived from ethylenicallyunsaturated comonomers which do not contain maleimide groups may also bepresent.

The molecular weight may be from 1000 to 200,000, preferably from 10,000to 100,000 and, most preferably, from 10,000 to 50,000. The copolymersare preferred.

A as linear or branched alkylene may contain preferably 2 to 4 carbonatoms and may be e.g. 1,6-, 1,5-, 1,4-, 1,3- or 1,2-hexylene, 1,5- or1,3- or 1,2-hexylene, 1,5- or 1,3-pentylene, 1,4-, 1,3- or 1,2-propyleneand ethylene. A is preferably propylene and most preferably ethylene.

R¹ and R² as alkyl may be linear or branched and contain preferably 1 or2 carbon atoms. Examples are n-butyl, isobutyl, tert-butyl, n-propyl,isopropyl, ethyl and methyl. R¹ and R² may also be unsubstituted or C₁-C₄ alkyl-substituted, especially methyl-substituted, tetramethylene,pentamethylene or 3-oxapentylene. D as C₁ -C₄ alkyl may have themeanings assigned to R¹ and R² and is preferably methyl or ethyl.

R³ as alkylene may be linear or branched and contain 2 to 18, preferably2 to 12 and most preferably 2 to 6 carbon atoms, and as oxaalkylene maycontain 2 to 6, preferably 2 to 4, carbon atoms. Examples are: ethylene,1,2- or 1,3-propylene, 1,4- or 1,3-butylene, pentylene, hexylene,octylene, decylene, dodecylene, octadecylene, decylethylene,tetradecylethylene, hexadecylethylene and 3-oxapentylene.

R⁴ as alkyl may be linear or branched. R⁴ is preferably a hydrogen atom.

The radical R⁵ preferably contains up to 12 carbon atoms. R⁵ as analiphatic radical is preferably linear or branched alkylene which may beinterrupted by hetero atoms such as O, S and NR⁴. The preferredsignificance of R⁵ in this case is alkylene and oxaalkylene containing 1to 12 carbon atoms. R⁵ as a cycloaliphatic radical preferably contains 5or 6 ring carbon atoms and is in particular cyclopentylene andcyclohexylene, each unsubstituted or substituted by 1 to 4 C₁ -C₄ alkylgroups, e.g. methyl. 1,3-Cyclohexylene and 1,4-cyclohexylene areparticularly preferred.

R⁵ as an aromatic hydrocarbon radical may be e.g. a carbocyclic aromaticradical containing preferably 6 to 16 carbon atoms or an araliphaticradical containing preferably 7 to 16 carbon atoms. Examples are 1,2-,1,3- and 1,4-phenylene, 1,3-toluylene, 1,7- and 2,7-naphthylene, 1,2-,1,3- or 1,4-benzylene and bicyclic aromatic groups of the formula##STR5## wherein Q is a direct bond, --O--, --S--, --SO--, --SO₂ --,--CO, ##STR6## --NR⁴ --, C₁ -C₆ alkylene, C₂ -C₆ alkylidene orcycloalkylidene containing 5 or 6 ring carbon atoms. The free bonds arepreferably in the 4,4'-position.

R⁵ is a heterocyclic-aliphatic or heterocyclic-aromatic radical maycontain 4 to 12 carbon atoms. Such radicals are preferably 5- or6-membered rings containing 1 or 2 hetero atoms such as N or O.

In the polyoxaalkylene radical R⁶, x is preferably a value from 1 to 12,most preferably from 1 to 6, and R⁴ is a hydrogen atom or methyl.

T₁ and T₂ are preferably methyl and tetramethylene.

Z.sup.⊖ is preferably the anion of a quaternising agent such as e.g. F,Cl, Br, SO₄, C₁ -C₄ alkyl-OSO₃, and sulfonate. The sulfonate anion maybe derived e.g. from aliphatic, cycloaliphatic and aromatic sulfonicacids, e.g. methylsulfonic, ethylsulfonic, propylsulfonic,butylsulfonic, pentylsulfonic, hexylsulfonic, cyclohexylsulfonic,phenylsulfonic, benzylsulfonic, toluylsulfonic or naphthylsulfonic acid.

A preferred subgroup of structural units of the formula I comprisesthose in which Y is an oxygen atom, A is linear C₂ -C₄ alkylene,preferably ethylene, R¹ and R² are C₁ - or C₂ alkyl, especially methyl,and D is a radical of the formula ##STR7## wherein R⁶ is ethylene,3-oxapentylene or 1,3-propylene, and T₁ is methyl; and Z.sup.⊖ is ahalide anion, preferably the chloride anion. If the polymers of theinvention are copolymers, these latter preferably contain, in additionto the chain members which carry maleimide groups, those chain memberswhich are derived from the following comonomers which do not containmaleimide groups: α-olefins, vinyl halides, e.g. vinyl bromide, vinylchloride and vinyl flouride; vinylidene, e.g. vinylidene chloride;nitriles of α,β-unsaturated acids, e.g. acrylonitrile ormethacrylonitrile; α,β-unsaturated acids, the esters or halogenderivatives thereof, e.g. acrylic acid, methacrylic acid, crotonic acid,maleic acid, methyl methacrylate, ethyl acrylate, propyl acrylate, butylacrylate, octyl acrylate, 2-ethyl-hexylacrylate, ethyl methacrylate,isopropyl methacrylate, dimethylaminoethyl methacrylate,diethylaminoethyl acrylate, glycidyl methacrylate, glycidyl acrylate orchloromethyl methacrylate, α,β-unsaturated carboxamides and theirderivatives, e.g. acrylamide, methacrylamide; aromatic vinyl compounds,e.g. styrene, methylstyrene, vinyl toluene or α-chlorostyrene; vinylketones, e.g. methyl vinyl ketone; vinyl esters, e.g. vinyl acetate;heterocyclic vinyl compounds, e.g. vinyl pyridine, vinyl pyrrolidone;and vinyl ethers.

Ethylenically unsaturated comonomers which contain the maleimide groupsdefined above are also suitable. Such comonomers can also be used if Dis not C₁ -C₄ alkyl. Such comonomers are described e.g. in GermanOffenlegungsschrift 26 26 769 and in European patent application 0 021019. They are substantially acrylates and methacrylates, acrylamides andmethacrylamides as well as vinyl ethers, which contain the maleimidegroup linked to the ester, amide or ether group respectively. Preferredcomonomers are those of the formulae ##STR8## wherein R, R⁴, R⁵, R⁶ andT₁ are as defined above and R⁷ has the same meaning as R⁵ or is --CO--R⁵--, and y is 1 or 2.

The polymers of this invention contain preferably 10 to 100 mole %, mostpreferably 40 to 100 mole %, of structural units containing maleimidylgroups of the formula ##STR9## The polymers preferably contain 5 to 90mole %, most preferably 10 to 60 mole %, of the structural units of theformula I.

The use of different comonomers makes it possible to impart desiredproperties to the polymers of this invention, e.g. light sensitivity,glass transition temperature, hydrophilic properties, hydrophobicproperties, affinity for dyes and solubility.

The properties of the present invention may be prepared by differentknown methods.

In one embodiment of the invention, homopolymers and copolymerscontaining at least one ethylenically unsaturated comonomer whichcontains a maleimidyl group for D=C₁ -C₄ alkyl, and containingstructural units of the formula II or III ##STR10## are reacted with aquaternising agent of the formula DZ or R² Z, in an organic solvent andoptionally with heating, to a temperature of about 100° C. The startingpolymers are obtained by known polymerisation methods from thecorresponding monomers and, where required, comonomers, described e.g.in German Offenlegungsschrift 26 26 769.

The quaternising agents DZ are novel and also constitute an object ofthe invention. They are prepared by known methods, e.g. by esterifyingor amidating compounds of the formula ##STR11## with haloacetic acid ortheir ester- or amide-forming derivatives. The reaction withhydroxyacetic acid gives corresponding hydroxy derivatives which, aswell as compounds of the formula ##STR12## can be converted in knownmanner into halogen derivatives, sulfonates and sulfates.

In a further embodiment of the process for preparing the polymers of theinvention, unsaturated monomers of the formula IV ##STR13## optionallytogether with at least one ethylenically unsaturated comonomer whichcontains a maleimidyl group for D=C₁ -C₄ alkyl, can be polymerised inorganic solution, in a manner known per se, in the presence of a radicalinitiator, e.g. azobisisobutyronitrile, in the temperature range fromabout 40° to 120° C.

The compounds of the formula VI, in which D is not C₁ -C₄ alkyl, andwhich are obtained by quaternisation of compounds of the formula##STR14## with DZ, are novel and likewise constitute an object of theinvention.

In a particularly advantageous embodiment, the polymers of thisinvention can be prepared by a novel process which also constitutes anobject of the invention. This process comprises polymerising a monomerof the formula V or VI ##STR15## by itself or together with at least oneethylenically unsaturated comonomer which contains a maleimidyl groupfor D=C₁ -C₄ alkyl, in organic solution and in the presence of a radicalinitiator and a quaternising agent DZ or R² Z. The polymers can thus beprepared economically in a single process step by simultaneouspolymerisation and quaternisation without any possible crosslinkingreactions being observed. To carry out the reaction, the reactants areheated with a radical initiator, such as azobisisobutyronitrile, in anorganic solvent. The temperature depends substantially on the radicalinitiator employed and may be e.g. in the range from 40° to 120° C.

Examples of suitable solvents for the process are alcohols such asmethanol, ethanol and methyl cellosolve, as well as polar aproticsolvents. The solvents may be employed singly or in mixtures of at leasttwo solvents. Examples are: ethers such as diethyl ether, dibutyl ether,tetrahydrofuran, dioxan, methyl ethylene glycol, dimethyl ethyleneglycol, dimethyl diethylene glycol, diethyl diethylene glycol, dimethyltriethylene glycol; halogenated hydrocarbons such as methylene chloride,chloroform, carbon tetrachloride, 1,2-dichloroethane,1,1,2-trichloroethane, 1,1,2,2-tetrachloroethane, carboxylates andlactones such as ethyl acetate, methyl propionate, ethyl benzoate,2-methoxyethyl acetate, γ-butyrolactone, γ-valerolactone andmevaloactone; carboxamides and lactams such as formamide, acetamide,N-methylformamide, N,N-dimethylformamide, N,N-diethylformamide,N,N-dimethylacetamide, N,N-diethylacetamide, γ-butyrolactam,γ-caprolactam, N-methylpyrrolidone, N-methylcaprolactam,tetramethylurea, hexamethylphosphoric amide; sulfoxides such asdimethylsulfoxide, tetramethylsulfoxide; sulfones such asdimethylsulfone, diethylsulfone, trimethylenesulfone,tetramethylenesulfone; primary, secondary and tertiary amines such asmethylamine, ethylamine, propylamine, pyrrolidine, piperidine,morpholine, dimethylamine, diethylamine, methylethylamine,trimethylamine, triethylamine, N-methylpyrrolidine, N-methylpiperidine,N-methylmorpholine; substituted benzenes such as chlorobenzene,nitrobenzene and cresol.

The polymer solutions, optionally after dilution and addition ofconventional additives, can be used as light-sensitive coatingcompositions. However, the polymer can also be isolated from thesolutions by conventional methods, e.g. by precipitation with anon-solvent, concentration by freezing, or distilling off the solvent.The polymers and their solutions are storage stable.

Owing to the presence of maleimide groups, the polymers of thisinvention are particularly suitable for crosslinking under the action ofelectromagnetic waves. The crosslinking results in the formation ofinsoluble products. Relief images can be obtained by imagewise exposureand subsequent development (dissolving out the uncrosslinked andunexposed polymer component). In addition to being used as photographicmaterial, the polymers can also be used for the surface protection ofdifferent substrates such as plastics, metals, glass, wood and ceramics.The polymers adhere well to the substrates.

Conventional additives which do not adversely affect thelight-sensitivity may be incorporated in the polymers or thecorresponding coating compositions. Examples of such additives aredulling agents, crosslinking agents and levelling agents, fillers, dyesor pigments, flame retardants, light stabilisers and antioxidants.

Without sensitisers, the polymers of the present invention have amaximum light sensitivity in the range from 200 to 320 μm. The lightsensitivity can be appreciably increased by appropriate choice ofsensitisers and can be optimally adapted to the light of differentcommercially available copying lamps, e.g. metal halide lamps.

Suitable sensitisers are described in German Offenlegungsschrift 26 26769. Preferred sensitisers are substituted thioxanthones which aredisclosed e.g. in German Offenlegungsschrift 30 18 891, e.g. alkylesters of 3-carboxy-7-methylthioxanthone. The sensitisers are preferablyemployed in amounts from 0.5 to 10% by weight, based on the polymer.Mixtures of different sensitisers can also be used.

The invention also relates to the light-sensitive materials obtainedfrom the polymers of this invention. Such materials are e.g.photographic recording materials for the printing industry, formes,special offset formes, as well as materials for the field ofphotomanufacture in electronics, e.g. photoresists for the production ofprinted circuits.

To this end the polymers are dissolved in organic solvents and, afterthe addition of different auxiliaries, applied to the supports. Thesupports are those customarily employed for the respective field ofapplication. For photographic recording materials the supports are e.g.polyester or cellulose acetate sheets or plastic-coated papers; foroffset forms, specially treated aluminium is used, while copper-cladlaminates are used for making printed circuits.

Coating can be effected by conventional known methods, e.g. byimmersion, knife-coating, curtain coating, brush coating, spraying andreverse roller coating.

After the coating application, the solvent is removed by drying to givea non-tacky, solid layer of light-sensitive polymer on the support.After conventional imagewise exposure of the material through aphotomask, the unexposed areas of the polymer are removed by dissolvingthem out in a developer and the polymer relief, consisting ofcrosslinked polymer, is revealed.

The preferred developer is ordinary mains water. In addition to water,however, it is also possible to use mixtures of water withwater-miscible organic solvents (alcohols, ketones, esters) and, incertain cases, also organic solvents, e.g. ethyl alcohol. Thetemperature of the developer solution can vary from +5° C. to about 90°C., preferably from 15° to 60° C. The developing time depends on thelayer thickness and the composition of the polymer, and can be fromabout 10 seconds to about 10 minutes. Images of good adherence andexcellent quality are obtained.

The following Examples illustrate the invention in more detail.

(A) PREPARATION OF THE INTERMEDIATES Example 1N-(chloromethylcarbonyloxyethyl)dimethylmaleimide ##STR16##

With stirring, 169.2 g (1 mole) of N-(2-hydroxyethyl)dimethylmaleimide,113.4 g (1.2 moles) of chloroacetic acid and 11.8 g of concentratedsulfuric acid are heated to reflux in 1000 ml of toluene using a waterseparator. The formation of water ceases after about 2 hours and 18 mlhave separated. The reaction solution is washed with saturated sodiumbicarbonate solution and water. The organic phase is dried overmagnesium sulfate and concentrated in a rotary evaporator at 40° C. Theresidue is dried for 2 hours at 60° C./0.1 mm, affording 206 g of acolourless liquid.

Elemental analysis: C₁₀ H₁₂ ClNO₄ (245.67): cal.: C 48.89; H 4.92; N5.70; found: C 48.88; H 5.05; N 5.58

Example 2N-(chloromethylcarbonyloxy-2,2-dimethylpropyl)dimethylmaleimide##STR17##

A mixture of 105.6 g (0.5 mole) ofN-(2,2-dimethyl-3-hydroxypropyl)dimethylmaleimide, 56.7 g (0.6 mole) ofchloroacetic acid, 5.9 g of concentrated sulfuric acid and 400 ml oftoluene are heated as described in Example 1 until the formation ofwater (9 ml) has ceased. The reaction solution is worked up as inExample 1, affording 121 g of a colourless liquid.

Elemental analysis: C₁₃ H₁₈ ClNO₄ (287.75): cal.: C 54.27; H 6.31; N4.87; Cl 12.32; found: C 54.24; H 6.13; N 4.92 Cl 12.13

Example 3 N-(chloromethylcarbonyloxy-3-oxapentyl)dimethylmaleimide##STR18##

A mixture of 90.6 g (0.41 mole) ofN-(5-hydroxy-3-oxapentyl)dimethylmaleimide, 46.6 g of chloracetic acid,4.8 g of concentrated sulfuric acid and 400 ml of toluene are reactedand worked up as described in Example 1, affording 112 g of a slightlyyellowish liquid.

Elemental analysis: C₁₂ H₁₆ ClNO₅ (289.72): cal.: C 49.75; H 5.57; N4.84 Cl 12.24; found: C 50.00; H 5.58; N 5.01 C 12.13.

Example 4 N-(chloromethylcarbonyloxyhexyl)dimethylmaleimide ##STR19##

(a) In a 500 ml glass round-bottomed flask equipped with magneticstirrer and reflux cooler, a mixture of 104.7 g (0.83 mole) ofdimethylmaleic anhydride, 96.7 g (0.81 mole) of 6-amino-1-hexanol and100 ml of toluene is stirred for 4 hours at reflux temperature. Volatileconstituents are first removed from the reaction solution in a water jetvacuum (bath temperature up to 100° C.), and then the solution isfractionated over a short column in an oil pump vacuum. The mainfraction consists of 176 g of N-(6-hydroxyethyl)dimethylmaleimide in theform of a colourless oil with a boiling point of 130° to 141° C./0.05mm.

(b) A mixture of 67.6 g (0.30 mole) ofN-(6-hydroxyhexyl)dimethylmaleimide, 34.0 g (0.36 mole) of chloroaceticacid, 3.5 g of concentrated sulfuric acid and 300 ml of toluene isreacted and worked up as described in Example 1. The residue consists of86.6 g of a colourless oil.

Elemental analysis: C₁₄ H₂₀ ClNO₄ (301.77): cal.: C 55.72; H 6.68; N4.64 Cl 11.75; found: C 56.80; H 6.79; N 4.34 Cl 11.55.

(B) PREPARATION OF THE POLYMERS Example 5 (a) Copolymer ofmethylmethacrylate (MMA) and dimethylaminoethylmethacrylate (DMAEMA)(molar ratio of the monomers: MMA/DMAEMA=1.8:1.0)

A thermostatically controllable double-jacket glass reactor equippedwith stirrer, thermometer, vacuum connection and nitrogen inlet ischarged with the following mixture:

36.0 g of MMA

31.4 g of DMAEMA

270.0 g of ethanol

0.337 g of azobisisobutyronitrile (AIBN).

Oxygen is removed by repeated evacuation and blanketing with purenitrogen. The polymerisation is initiated by heating to a temperature of60°±1° C. in the flask and carried out for 24 hours at this temperature.The viscous polymer solution is precipitated in a total of 3500 ml ofwater by means of a mixer and the solid colourless polymer poweder isdried for 3 days in a vacuum drying cabinet at c.50° C./100 torr. Yield:59 g of polymer having an amine content of 2.68 val/kg (theory: 2.94val/kg).

(b) Quaternisation of the polymer

A mixture consisting of

10.0 g of the above polymer

8.6 g of N-(chloromethylcarbonyloxy-3-oxapentyl)dimethylmaleimideobtained in Example 3,

95.0 g of dimethylformamide

is heated in a glass flask equipped with magnetic stirrer for 1 hour at60° C. and then for 24 hours at 80° C. The yellowish viscous polymersolution is precipitated by stirring it vigorously into 2000 ml of ethylacetate and the precipitate is dried at 40° C. in a vacuum dryingcabinet with the exclusion of light.

Yield: 16.8 g of polymer powder which, when analysed, contains 4.3% ofCl. This corresponds to 1.21 val/kg of quaternary ammonium groups(theory: 1.51 val/kg). The polymer is soluble in water.

Example 6 Copolymer of MMA/DMAEMA in the ratio 1.8:1, quaternised withthe compound of Example 1

10.0 g of the polymer of Example 5a

7.3 g of N-(chloromethylcarbonyloxyethyl)dimethylmaleimide of Example 1

95.0 ml of dimethylformamide

are reacted as in Example 1(b).

Yield: 14.2 g of solid polymer which, when analysed, contains 4.5% ofCl. This corresponds to 1.27 val/kg of quaternary ammonium groups(theory: 1.62 val/kg). Inherent viscosity (0.5% in methyl cellosolve,25° C.)=1.04 dl/g.

Example 7 Polymerisation and quaternisation

Polymer from: ##STR20## 500 ml glass ampoules equipped with magneticstirrer are charged with the mixtures listed below and the oxygen isremoved by repeated evacuation and blanketing with pure nitrogen. Theampoules are heated for 24 hours in a heating bath which isthermostabilised to 65° C., then cooled, and the contents are pouredinto 2000 ml of ether. The polymers are obtained as rubbery substances.The ether is removed by decantation, then fresh ether is added and thepolymer is dried at 40° C./100 mm in a vacuum drying cabinet. Thecombined ether phases are concentrated by rotary evaporation, theresidue is weighed and yield is calculated therefrom.

7.1

28.1 g of DMI-o-MA

4.7 g of DMAEMA

8.7 g of the compound of Example 3

0.16 g of azobisisobutyronitrile

76.5 g of dimethylformamide

Yield=96%. The polymer is soluble in water.

7.2

28.1 g of DMI-o-MA

3.1 g of DMAEMA

5.8 g of the compound of Example 3

0.16 g of azobisisobutyronitrile

72.0 g of dimethylformamide

Yield=96%. The polymer is soluble in water.

7.3

28.1 g of DMI-o-MA

3.9 g of DMAEMA

7.2 g of the compound of Example 3

0.16 g of azobisisobutyronitrile

74.7 g of dimethylformamide

In contrast to 7.1 and 7.2, the polymer 7.3 is not precipitated inether. Instead, the reaction solution is further used direct for thepreparation of light-sensitive materials.

Example 8 Polymerisation and quaternisation

Polymer from ##STR21##

The following mixtures are polymerised as in Example 7:

8.1

23.7 g of DMI-MA

7.86 g of DMAEMA

12.28 g of the compound of Example 1

0.16 g of azobisisobutyronitrile

73.7 g of dimethylformamide

Cl content (after analysis)=4.9%, corresponding to 1.38 val/kg ofquaternary ammonium groups (theory: 1.14 val/kg).

8.2

23.7 g of DMI-MA

6.3 g of DMAEMA

9.83 g of the compound of Example 1

0.20 g of azobisisobutyronitrile

93.0 g of dimethylformamide

Yield=93%.

Example 9 Polymerisation and quaternisation

Polymer from ##STR22##

The following mixture is polymerised as in Example 7:

28.1 g of DMI-o-MA

3.1 g of DMAEMA

2.52 g of dimethylsulfate

0.16 g of azobisisobutyronitrile

72.8 g of dimethylformamide

Yield=97%. The polymer is soluble in water.

APPLICATION EXAMPLES

The sensitiser used in the following Examples and abbreviated to CMTX(3-carbethoxy-7-methylthioxanthone) has the following structure##STR23##

All tests are carried out under yellow light.

Example 10

The following coating solution is prepared:

4.0 g of quaternised polymer of Example 5

16.0 g of ethylene glycol monomethyl ether

0.200 g of CMTX.

Using a wire film applicator, this solution is coated to a wet filmthickness of 20 μm onto a biaxially stretched 100 μm polyester sheet anddried for 5 minutes at 85° C. The homogeneous, slightly yellowishlight-sensitive layer has a thickness of about 3-4 μm.

The films are exposed on a copying machine (Oce Helioprint 36, 1000 Wmetal halide lamp at a distance of 53 cm) for 30 seconds in contact witha test wedge.

The exposed strips are developed by immersing them for 30 seconds inlukewarm water (35° C.) and then for 3 minutes in a 2% aqueous solutionof the dye of the formula ##STR24## The strips are then washed for 15seconds in running water and dried. An intense orange image which has anoptical density of 1.7 at 465 μm is obtained.

Example 11

The following coating solution:

4.0 g of the quaternised polymer of Example 6

16.0 of ethylene glycol monomethyl ether

0.200 g of CMTX

is coated on polyester as described in Example 11, exposed, developedfor 30 seconds with water of 30° C. and coloured. An intense orangeimage which has an optical density of 3.1 at 465 μm is obtained.

Example 12

The following coating solution is prepared:

3.0 g of the polymer of Example 7.1

7.0 g of a 1:1 mixture of methanol/methylene chloride

0.060 g of CMTX.

This solution is coated with a wire film applicator to a wet filmthickness of 120 μm onto a copper-clad laminate which is used for makingprinted circuit boards, and dried for 20 minutes at 40° C. Thephotopolymer layer thickness of this coated printed circuit board isabout 35 μm. The board is exposed in the copying machine described inExample 10 through a partial wedge for 2 minutes and developed bywashing for 2 minutes in running water of 30° C.

The series of conductors can then be reinforced on this board in knownmanner by deposition of copper in a galvanising bath, without thephotoresist being attacked. Subsequently the photoresist can be strippedoff by treatment with warm 5% sodium hydroxide solution.

Example 13

The following coating solution is prepared:

4.0 g of the polymer of Example 7.2

16.0 g of ethylene glycol monomethyl ether

0.320 g of CMTX.

Using a wire film applicator, this solution is coated to a wet thicknessof 20 μm onto a copper-clad laminate which is used for making printedcircuit boards, and dried for 3 minutes at 85° C. The circuit board isexposed for 30 seconds as in Example 10 and developed by agitating it inwater of 35° C. for 2 minutes. Then the printed conductor pattern isproduced by cauterising in known manner with iron(III) chloride. Thephotoresist is not attacked by the caustic solution. If desired, it canbe stripped off by treatment with warm sodium hydroxide solution.

Example 14

The following coating solution is prepared:

20.0 g of the polymer solution in dimethylformamide prepared as inExample 3

0.140 g of CMTX

0.420 g of citric acid.

Using a wire film applicator, this solution is coated to a wet filmthickness of 120 μm onto a copper-clad laminate used for making printedcircuit boards, and dried for 25 minutes at 85° C. The board is exposedfor 3 minutes as in Example 10 and developed for 2 minutes with water of35° C. using a hand spray. The developed photoresist can then be used asa galvanoresist as in Example 12. It withstands very well attack by thestrongly acidic galvanising bath and gives printed conductor patterns ofhigh quality.

What is claimed is:
 1. A compound of formula VII

    D--Z                                                       (VII)

wherein Z is chloro or bromo, and D is a maleimidyl radical of theformula ##STR25## wherein R⁶ is alkylene containing 2 to 12 carbon atomsor is ##STR26## where x is an integer from 1 to 6, and R⁴ is hydrogen ormethyl.
 2. The compound according to claim 1 wherein Z is chloro and R⁶is ethylene.
 3. The compound according to claim 1 wherein Z is chloroand R⁶ is 2,2-dimethyl-1,3-propanediyl.
 4. The compound according toclaim 1 wherein Z is chloro and R⁶ is 3-oxapentamethylene.
 5. Thecompound according to claim 1 wherein Z is chloro and R⁶ ishexamethylene.